Alkoxy acrylonitriles and process of preparing the same



. follows:

CHzBr-CHBr-OR-i-CuCN CHzBt-CHCN-l-ChBt Patented Aug. 10,1943 4 loot CorporatiomAkr-on, Ohiog-acorporathihof. Delaware v No Drawing". "Application Juarez 5,1911, i 't SerialNo.39,9, 677 momma. (01.26944691 This invention relates to certain new com;-

pounds of unsaturated nature and to a method of preparing the same. More particularly, it"

relates to substituted'nitriles of the acrylic se ries and of the propionic series. I

Investigations looking to the discovery of compounds suitable in polymerizationshave led to the preparation of certain I substituted acrylonitriles which are new. In the. course ofthis preparation, substituted propionitriles'. are

produced which are also new. Boththe acry-.'

lonitriles and the propionitriles carry an oxygencontaining substituent and hence, the new compounds consist of acrylonitriles and propionitriles substituted in the alpha position an aliphatic oxy group.

The new compounds include such acrylonitriles as alpha methoxy acrylonitrile', alpha ethoxy acrylonitrile, alpha n-propoxy acrylonitrile, 'alph'a isopropoxy acrylonitrile, alpha nbutoxy acrylonitrile, alpha isobutoxy acrylonitrile, alpha n-arnyloxy acrylonitrile and alpha isoamyloxy acrylonitrile. Propionitriles included are, for example, beta brom, alpha methoxypropionitrile, beta brom, alpha ethoxy propionitrile,

etc. I

The new compounds'can be prepared by first treating an alpha beta dibromo dialiphatic, ether with a cyanide to replace one atom of bromine with a nitrile radicalto form an alpha cyano beta bromo ether or beta bromo, alpha (aliphatic 'oxy) propionitrile. This cyano ether is then treated with a dehydrobrominating agent, such as pyridine or quinoline, to remove hydrogen bromide, thus leaving the final product, an alpha (alphatic oxy) acrylonitrile. Employing cuprous cyanide in the first step andpyrldine in the second step, the equations for the reactions are as To illustrate the process, the following examples are given:

EXAMPLE 1 Beta brom alpha. ethoxy propz'onitrile To a suspension of 147 grams of CuCN and V 300 cc. of anhydrous ethyl ether was added, with stirring, over a period of one hour and 20 minutes, 378 grams of alpha, beta dibromethyl ethyl The ma n portion distilled at 75-76 c./'z had a density of -dz1=1.5410;' and an index of re -Q.

. pionitrile;

for. another hour and.

219.7 grams y'oi' having the following properties: a

'Exsmrnaz' q Alpha 8m (rcryloaitrile .There was taken l78" gran 1s'..ot prepared above, beta brom, alphayethoxypro pionitrile, which was mixed with- 100 grams of 1 pyridine and 2.0 gramsofdiphenyl para phen- I v ylene diamine (antioxidant). The. mixture was heated for 1% to 2 hours on'asteam bath in a flask fitted with a reflux. condenseia At the end of this period, the product was distilled ut .01 the reaction mixture underreduced pressure and was washed with dilute hydrochloric acidzto remove unreacted pyridine. .The crude product. was dried and fractionated under reduced pres-'- sure to obtain a yield 01' 67 grams of alpha acrylonitrile,

. Qll =Q-'CN The substance had theiollowing properties:

'* EXAMPLE 3 In accordance with theprocedurerollowedr in Example 1 above, 773.5 grams of alpha, beta-die bromethyli methyl ether was "reactedwith 319 grams of CuCN. A yieldjof 337.2- g'rams ofcrude I beta brom, alpha methoxypropionitrile was ob-,-I

tained having'the formula.

. 'cmm-cn cn fraction pr np 7=1.4658 l Alpha methozy'acrylonitrile 1 mm 158mm h tabromiaipha mfethoxvf ether. Th we was stirred and refluxed. Dropionitrile obtai in dedI A m." h

i ether was distilled ofli. he-crude productwas dis-5 .1

tilled joutot thegreactio'n mixture under-reduced; "i pressure. Fractionation of the 1 distillate; .gavefi 4 beta 'brom; alpha ethoxy .pro-

the product ethoxy 103 grams of pyridine and the reaction conducted in the same manner as that described in Example 2.- There was obtained 52.2 grams oi alpha mcthoxy acrylonitrile:

CHFC-CN om having the following properties:

B. P. (50 mm.) =48-51' 0., B. P. (744 mm.)=

Exmu

Beta brom, alpha butozy propionitrile A mixture or 735 grams of alpha, beta dibromethyl n-butyl ether and 185 grams oi. CuCN was reacted in the manner employed in Example 1 above. A yield 01' 331 grams of product was obtained, of which the main portion distilled at To 316 grams of the product obtained in Example 5, beta brom, alpha n-butoxy propionitrile,- was added 154 grams of pyridine and the procedure described in Example 2 was followed to obtain 103.4 grams of product. This was alpha n -butoxy acrylonitrile,

having the following characteristics: B. P. 84- 86 C. 30 mm.; das=0.8863; nn =1.4'722.

All of the compounds described in Examples l-6 inclusive are new. The class includes as well other alpha (aliphatic oxy) nitriles or the acrylic series, especially the alpha alkoxy acrylonitriles,

and other alpha (aliphatic oxy) beta halo proplonitriles, particularly the alpha alkoxy beta brom propionitriles such as beta brom alpha propoxy propionitrile. All or these may be prepared by one or the other 0! the above procedures or modifications thereof.

While there have been described above the preferred embodiments of the invention, it will be apparent to those skilled in the art that various modifications and changes may be made therein without departing from the spirit of the invention or from the scope of the appended claims.

I claim:

1. The alpha (aliphatic oxy) acrylonitriles.

2. The alpha alkoxy acrylonitriles.

3. Alpha ethoxy acrylonitrile.

4. Alpha methoxy acrylonitrile.

5. Alpha n-butoxy acrylonitrile.

6. A method of preparing alpha alkoxy acrylonitriles which comprises treating an alpha, beta dibromo ethyl alkyl ether with a cuprous cyanide and then treating the resulting beta bromo alpha alkoxy propionitrile with a dehydrobrominating agent.

7. A method of preparing alpha alkoxy acrylonitrile which comprises treating an alpha, beta dibromo ethyl alkyl ether with cuprous cyanide and then treating the resulting beta bromo alpha alkoxy propionitrile with a tertiary amine.

8. A method of preparing alpha ethoxy acrylonitrile which comprises treating alpha, beta dibrom ethyl ethyl ether with cuprous cyanide, treating the resulting beta brom alpha ethoxy propionitrile with pyridine and separating the alpha ethoxy acrylonitrile.

9. In a method of preparing alpha alkoxy acrylonitriles, the step which comprises treating a beta bromo alkoxy propionitrile with a dehydrobrominating-agent.

10. In a method .of preparing alpha alkoxy acrylonitriles, the step which comprises treating a beta bromo alpha alkoxy propionitrile with a tertiary amine to split out hydrogen bromide.

JOHN R. LONG. 

